Patent GB-358421-A (GB)
Title: Improvements in and relating to colouring matters and intermediates of the anthraquinone series
IPC: C09B5/34
Filed: 1930-04-01
Abstract: Diphthaloylacridones; anthraquinonylaminobenzoylbenzoic acid derivatives.-Vat dyes are prepared by treating with an acid condensing agent, for example sulphuric acid, a compound of the formula <FORM:0358421/IV/1> wherein AQ represents a 1 : 2- or 2 : 3-anthraquinonylene residue and X an amino-, substituted amino-, hydroxy, ether, mercapto, or thioether group.  Instead of sulphuric acid, oleum, aluminium chloride, acetic anhydride or other acid condensing agents may be employed.  The products give deeper shades than those derived from substances of the above formula wherein X represents hydrogen or a methyl group (see Specification 894/11, [Class 2 (iii), Dyes &c.]. The compounds of the above formula are obtained by condensing a 1.2- or 2.1- or 2.3 halogenanthraquinone carboxylic acid with a 2-benzoylbenzoic acid of the formula: <FORM:0358421/IV/2> wherein X has the significance given above.  The two acids are preferably condensed in an alkaline medium in presence of acid absorbers such as soda ash, and a copper catalyst; or they may be condensed in an organic medium (nitrobenzene) in presence of suitable acid absorbers, such as pyridine; or the acid esters may be condensed together in an organic medium.  In examples (1) 31-amino-41-phenoxy-2-benzoylbenzoic acid is condensed with 1-chloranthraquinone -2-carboxylic acid; the product is ring-closed by means of sulphuric acid and then dyes cotton reddish-brown shades: (2) 31-amino-41-anilino-2-benzoylbenzoic acid is condensed with 1-chloranthraquinone-2-carboxylic acid; the product is ring-closed by means of strong sulphuric acid and then dyes cotton greenish-blue shades: (3) 31-amino-41-methylamino-2-benzoylbenzoic acid is condensed with 1-chloranthraquinone-2-carboxylic acid; the product is ring-closed by means of sulphuric acid and then dyes cotton blue shades: (4) 31-amino-41-p-aminophenylamino-2-benzoylbenzoic acid is condensed with 1-chloranthraquinone-2-carboxylic acid; the product is ring-closed by means of strong sulphuric acid and then dyes cotton blueish-green shades: (5) 31-amino-41-anthraquinonylamino-2-benzoylbenzoic acid is condensed with 1-chloranthraquinone-2-carboxylic acid; the product is ring-closed by means of sulphuric acid and then dyes cotton dark green shades: (6) 31-amino-41-benzoylamino-2-benzoylbenzoic acid is condensed with 1-chloranthraquinone-2-carboxylic acid; the product is ring-closed by means of sulphuric acid monohydrate and then dyes blueish-grey shades; it appears to be an aminodiphthaloylacridone which is converted by benzoylation into a very fast dye: (7) 31-amino-41-hydroxy-2-benzoylbenzoic acid is condensed with 1-chloranthraquinone-2-carboxylic acid; the product is ring-closed by means of sulphuric acid monohydrate and then dyes cotton blueish-red shades: (8) 31-amino-41-mercapto-2-benzoylbenzoic acid is condensed with 1-chloranthraquinone-2-carboxylic acid; the product is ring-closed by means of monohydrate and then dyes cotton blue shades: (9) 31-amino-41-methylamino-2-benzoylbenzoic acid is condensed with 2-chlor-anthraquinone-3-carboxylic acid; the product is ring-closed by means of monohydrate and then dyes cotton blueish-green shades; (10) 31-amino-41-benzoylamino-2-benzoylbenzoic acid is condensed with 2-chloranthraquinone-3-carboxylic acid; the product is ring-closed by means of monohydrate and then dyes cotton yellowish-green shades: (11) 31-amino-41-anilino-2-benzoylbenzoic acid is condensed with 2-chloranthraquinone-3-carboxylic acid; the product is ring-closed by means of monohydrate and then dyes cotton greenish-grey shades.  31 Amino-2-benzoylbenzoic acids of the second formula above containing in the 41-position the specified substituents are prepared as follows: The 41-anilino, 41-methylamino, 41-p-aminophenyl aminoderivatives are prepared by reacting 31-nitro-41-chloro-2-benzoylbenzoic acid with aniline, methylamine and p-phenylenediamine respectively, and reducing the nitro group by means of ferrous sulphate and ammonia.  The 41-anthraquinonylamino derivative is prepared by saponifying the methyl ester of 41-anthraquinonylamino-31-nitro-2-benzoylbenzoic acid (see Example 1 of Specification 334,872, [Class 2 (iii), Dyes &c.]), and reducing the nitro group by means of sodium hydrosulphite. The 41-benzoylamino derivative is prepared by benzoylating 41-amino-31-nitro-2-benzoylbenzoic acid and reduction by means of ferrous sulphate and ammonia.  The 41-phenoxy derivative is prepared by reacting 31-nitro-41-chloro-2-benzoylbenzoic acid with phenol and reducing the product by means of sodium hydrosulphite.  The 41-mercapto derivative is prepared by reacting 31-nitro-41-chloro-2-benzoylbenzoic acid with potassium sulphide.